JPH07248413A - Production of color filter - Google Patents

Abstract

PURPOSE:To obtain enough flatness and to improve the display quality by forming a black matrix and pixels on a transparent substrate in such a manner that either surface of the black matrix or pixels has repellency against water and oil and then treating the substrate to remove the repellency against water and oil. CONSTITUTION:After a black matrix and pixels are formed on a transparent substrate in such a manner that either surface of the matrix or pixel has repellency against water and oil, the substrate is treated to remove the repellency against water and oil. By this method, such a component that is repellent against ink is deactivated so that the repellency against a top coating material can be eliminated. Thus, enough flatness can be obtd. by applying a top coating material. Thereby, the color filter is made flat and excellent display quality is obtd. Even when a top coating material is not applied, no adverse effect such as to disturb the orientation of the liquid crystal in the module and to cause insulation fault is exerted because the component which is repellent against ink is deactivated. Thus, high reliability is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter mainly used for liquid crystal display devices.

[0002]

2. Description of the Related Art A color filter for a liquid crystal display device is composed of a large number of picture elements each having pixels of three primary colors of red, green and blue formed on a transparent substrate as one picture element. A light-shielding region (generally referred to as a black matrix in black) having a certain width is provided between each pixel in order to increase the display contrast and to prevent the TFT from being exposed to light. Usually, after forming a black matrix and pixels, a top coat (surface protective layer) is provided on the glass substrate for the purpose of protecting and flattening the pixel portion.

Color filter manufacturing methods include a method of dyeing a dyeable medium formed by a photolithography method, a method of using a pigment-dispersed photosensitive composition, an electrodeposition method of using a patterned electrode, and a low-cost method. As a cost manufacturing method, there are a printing method, an inkjet method of forming a colored portion by using an inkjet type ink jet device, and the like.

Among the conventional manufacturing methods, the printing method and the ink jet method have a smaller number of steps and a lower cost than the dyeing method and the pigment dispersion method in which pixels are formed by photolithography one by one. There is a drawback in that bleeding and color mixing of pixels in the area cannot be avoided and the quality of the color filter is inferior.

In order to obtain a high-quality color filter at a low cost, it is essential to prevent ink bleeding and color mixing by some means in the printing method or the inkjet method. JP-A-4-123005, JP-A-4-126006, JP-A-4-1230
07, JP-A-4-151604, and JP-A-4-195102 disclose a technique of suppressing the spread of ink by using an ink-repellent partition. Further, the present inventors have filed Japanese Patent Application No. 5-1827
60, Japanese Patent Application 5-182761, Japanese Patent Application 5-182762, Japanese Patent Application 5-182763
In the issue, we proposed improvements to these techniques. However, in this technique, since the partition fence has resilience against the top coat agent, there is a problem that sufficient flatness cannot be obtained by applying the top coat agent.

When a pixel is formed by photolithography, an ink-repellent black matrix is used, so that it is possible to form an accurate pixel pattern having no step on the black matrix. Japanese Patent Laid-Open No. 5-1730
15, Japanese Patent Publication No. 5-69201 discloses a technique for rendering the surface of the black matrix and / or the pixel portion water and oil repellent. However, in this technique, the black matrix and / or the pixel portion has a resilience against the top coat agent, so that there is a problem that sufficient flatness cannot be obtained by applying the top coat.

[0007]

SUMMARY OF THE INVENTION The present invention was devised in view of the above-mentioned drawbacks of the prior art. The object of the present invention is to use an ink-repellent black matrix and to obtain sufficient flatness. Another object of the present invention is to provide a method of manufacturing a color filter for a liquid crystal display device, which has a high display quality and is low in cost.

[0008]

The object of the present invention is as follows.
In a method for manufacturing a color filter in which pixels of a plurality of colors are formed at predetermined positions on a transparent substrate and a black matrix is formed in the gaps between the pixels, one of the surfaces of the black matrix and the pixels has water and oil repellency. And a substrate treatment step of eliminating the water / oil repellency after the formation.

A feature of the present invention includes a step of treating a substrate after forming a black matrix and pixels on a transparent substrate so that either surface has water repellency or oil repellency and then eliminating the water repellency or oil repellency. Especially. The purpose of the substrate treatment is to inactivate a water-repellent / oil-repellent component (hereinafter referred to as an ink repellent component) in the black matrix or pixels. By deactivating the ink repellent component,
Since the resilience to the top coat agent can be eliminated, sufficient flatness can be obtained by applying the top coat. Therefore, since the color filter can be made flat, the display quality is excellent. Even when the top coat is not applied, the ink repellent component is deactivated and does not disturb the alignment of the liquid crystal in the module or cause adverse effects such as insulation failure. Obtainable.

The method for treating the substrate is by heating, and by eluting the ink-repellent component with a solvent,
There is a material that loses water / oil repellency, but the material is not limited to these. It is effective that the heating is carried out at a thermal decomposition temperature at which 5 parts by weight of the ink repellent component is decomposed or higher, preferably for 1 hour or more, but it is not limited to this method. In the solvent treatment, a method in which a black matrix and pixels have resistance to a treatment solvent and an ink repellent component is soluble and a color filter is immersed in the solvent is effective, but is not limited to this. Not a thing. Although ethanol and isopropanol are effective as the solvent, the solvent is not limited to them.

The method for forming the black matrix and pixels is not particularly limited, but a black matrix having a water-repellent / oil-repellent surface is formed using an ink repellent resin composition, and the water-repellent / oil-repellent property is utilized. Pixels are preferably formed in the gaps of the black matrix. Specifically, in order to surely prevent ink bleeding and color mixture in the pixel forming process by a printing method or an inkjet method, the surface of the black matrix is 20 ° or more with respect to the blue ink for forming pixels during pixel formation. It is preferable to have ink repulsion with a receding contact angle of.

In order to form such a black matrix, a photosensitive black resin containing an ink repellent component is used, a method of pattern exposure and development, and a black resin containing an ink repellent component is applied onto a transparent substrate. After that, a photosensitive resin is laminated thereon, pattern exposure and development are performed, and the black resin is etched by using the obtained photosensitive resin pattern as a mask. After applying the black resin on the transparent substrate. However, the present invention is not limited to these methods, in which a photosensitive resin containing an ink repellent component is laminated, pattern exposure and development are performed, and the black resin is etched by using the obtained photosensitive resin pattern as a mask.
In the case of, the black matrix has a single layer structure which is black and has an ink repellent property, and in the case of, the black matrix has a two layer structure in which a layer having an ink repellent property is laminated on a black layer.

An important effect of using an ink-repellent black matrix having a receding contact angle of 20 ° or more with a colored ink is that the black resin is removed by utilizing the water / oil repellency of these ink-repellent components. Prevents ink from adhering to or exuding parts other than the part (partition fence), suppressing the deterioration of accuracy due to print blur and bleeding during printing, and when applying ink by the inkjet method, to other areas. This is to prevent the bleeding of the color and the color mixture with the adjacent color to maintain a high degree of independence of each color part. When the receding contact angle is 20 ° or less, it is difficult to obtain the above effects of the resin black matrix. When the ink adheres to the partition fence in the inkjet method, unevenness in the ink film thickness occurs between the ink and the non-adhered portion, resulting in uneven color in the pixel portion.

The ink repellent component preferably has an extremely low surface energy in order to obtain excellent resilience to the ink for forming pixels. Such low surface energy substances include fluorine-containing compounds and silicon-containing compounds. Are effective, but are not limited thereto.

The fluorine-containing compound includes a fluorine-containing group,
Examples thereof include monomers or oligomers having both a hydrophilic group and / or a lipophilic group, and polymer compounds having a fluorine atom.

Examples of monomers or oligomers having both a fluorine-containing group and a hydrophilic group and / or an affinity group include those represented by the general formulas (1) to (6), but are not particularly limited thereto. Not a thing. Among these, those represented by the general formulas (3) and (5) are particularly preferable.

[0017]

[Chemical 1] The polymer compound having a fluorine atom may be used by dissolving it in a black matrix (in the case where the black matrix has two layers, it means the layer containing the ink repellent component of the upper layer) or by mixing it in the molecular order. Both can be used by dispersing them as fine particles in a matrix. Examples of the one to be dissolved in the black matrix or mixed in the molecular order include polyvinylidene fluoride, fluoroolefin vinyl ether copolymer, trifluoroethylene-vinylidene fluoride copolymer, etc., which are dispersed as fine particles. Examples of the resin to be used include polytetrafluoroethylene, perfluoroethylene propylene resin, perfluoroalkoxy resin and the like, but are not particularly limited thereto.

As the silicon-containing composition, it is effective to use silicone fine particles containing polyorganosilsesquioxane having a repeating unit represented by the general formula (7) as a main component dispersed in a black matrix. .

[0019]

[Chemical 2] These fluorine-containing compounds and silicon-containing compounds can be used alone or in combination of two or more. It may also be used in combination with other ink repellent components.

As the resin forming the black matrix, it is conceivable to use a photosensitive resin or a non-photosensitive resin as described above. In either case, a resin excellent in heat resistance and chemical resistance is used. desirable.

As a resin having excellent heat resistance and chemical resistance,
Highly crosslinked resins, such as thermosetting acrylics,
Examples thereof include, but are not limited to, melamine resin, epoxy resin, alkyd resin, unsaturated polyester resin and the like, or those having a ladder structure, such as polyimide resin.

Examples of the thermosetting acrylic resin include acrylic acid, methacrylic acid, or esterified products thereof, which are obtained by copolymerizing styrene, vinyltoluene, vinyl acetate, acrylonitrile, etc., that is, what is generally called an acrylic resin, and a curing agent. As an isocyanate compound,
Examples thereof include those using melamine resin and epoxy resin, and those obtained by copolymerizing the above acrylic resin with a functional monomer such as N-methylolacrylamide, alkoxy-N-methylolacrylamide and the like.

As the melamine resin, an amino group (-NH
₂ ) Melamine with 1 to 6 hydrogenated hydrogen,
A water-soluble melamine resin consisting of the quantified product, for example, "Sumitex Resin" manufactured by Sumitomo Chemical Co., Ltd., or a melamine obtained by esterifying a methylol group with a C1 to C4 aliphatic alcohol, and an oil-soluble melamine resin composed of the quantified product, For example, "Super Beckamine" manufactured by Dainippon Ink and Chemicals, Inc., or polyester resin or acrylic resin crosslinked with melamine resin can be used.

The epoxy resin is bisphenol A.
Bisphenol A type epoxy resin, which is an oligomer or polymer obtained by the reaction of chlorophenol with epichlorohydrin, such as "Epomic" R140 of Mitsui Petrochemical Co., Ltd., or novolac type epoxy obtained by the reaction of novolac resin and epichlorohydrin Resins such as "DEN" 431 of Dow Chemical Japan Co., Ltd., or brominated epoxy resins which are oligomers or polymers obtained by the reaction of tetrabromobisphenol A or brominated phenol novolac with epichlorohydrin, such as Nippon Kayaku Co., Ltd. ) "B
REN "or glycidylamine type epoxy resin of carboxylic acid and epichlorohydrin, for example," Epomic "R508 of Mitsui Petrochemical Co., Ltd. or glycidylamine type epoxy resin of amines and / or aminophenols and epichlorohydrin For example, "SUMI-EPOXY" ELM-120 of Sumitomo Chemical Co., Ltd., or an alicyclic epoxy resin obtained by oxidizing an alicyclic compound having a double bond with peracid, for example, "Ar of CIBA"
and “Aldite” CY179 and the like.

As the alkyd resin, a fatty acid-modified alkyd resin comprising a fatty acid, a polybasic acid and a polyhydric alcohol,
Alternatively, there is an oil-free alkyd resin containing no fatty acid, and examples thereof include those which are crosslinked by a radical initiator of unsaturated fatty acids, and those which are cured by crosslinking with polyisocyanate or melamine.

As the unsaturated polyester resin, a polyester obtained by dissolving an unsaturated dibasic acid such as maleic anhydride or a derivative thereof and a polyhydric alcohol in a liquid vinyl monomer, or an epoxy resin containing acrylic acid or methacrylic acid Compound in which saturated monobasic acid is added dissolved in liquid vinyl monomer (vinyl ester resin)
And so on.

As the polyimide resin, a polycondensation type polyimide obtained by polycondensation of tetracarboxylic dianhydride and diamine, for example, "Semicofine" manufactured by Toray Industries, Inc., or one obtained by addition polymerization of maleimide or bismaleimide, For example, "Compim" by Technochemie.
id "751 and the like.

Examples of the photosensitive resin having excellent heat resistance and chemical resistance include, but are not limited to, photocrosslinkable acrylic resin, photosensitive polyimide, and novolac resin containing naphthoquinonediazide as a photosensitive group. is not.

Examples of the photocrosslinkable acrylic resin include a photocurable acrylic resin obtained by adding a polyfunctional acrylate, a monomer or an oligomer, and a photoinitiator to the acrylic resin.

Among the photosensitive polyimides, as the photocurable polyimide, a polyimide precursor varnish generally produced in a dipolar aprotic solvent by combining a tetracarboxylic acid and a diamine is used as a photosensitive group such as a methacryl group. A mixture of amino compounds having a group (for example, Japanese Patent Publication No. 59-52822), a group in which a dimerizable or photopolymerizable group is introduced by an ester bond by light (for example, US Pat. No. 3,957,512), N -A mixture of a methylol acridamide compound and a varnish of a polyimide precursor (for example, Proceedings of the Polymer Society of Japan, p807, 1990).
Year) or a mixture of a polyimide precursor varnish with an acrylic monomer (for example, Japanese Patent Laid-Open No. 2-50161).

Among the photosensitive polyimides, as the photo-soluble polyimide, a polyamic acid into which a photodegradable photosensitive group is introduced through an ester bond (for example, JP-A-1-61747).
), A polyamic acid to which a naphthoquinonediazide compound is added (for example, Proceedings of the Polymer Society of Japan, Vol. 40, No. 3, 8).
21 (1991)) and the like.

Examples of the novolak resin containing a naphthoquinonediazide derivative as a photosensitive group include, for example, a mixture of polyhydroxybenzophenone and an ester of o-naphthoquinonediazide sulfonic acid in a cresol novolac resin, or a naphthoquinone-1,2-phenol phenol novolac resin. Examples thereof include diazide-5-sulfonic acid ester.

As the coloring component contained in the black matrix, it is desirable to obtain a high light-shielding property, and in order not to impair the patterning property of the black resin layer by development or etching, it is fine particles having a particle size of 1 μm or less. Desirably, more preferably 0.1 μm or less. Examples of the fine particles having a high light-shielding property include, but are not limited to, carbon black, pigments, dyes, and fine particles of metal oxides such as Ti, Cr, and Ni.

The thickness of the black matrix is usually 0.05.
It is preferably ˜30 μm, and the optimum value can be determined from coating properties, pattern resolution, optical density (OD value) and the like. The OD value can be in the range of 0.5 to 4,
For the purpose of the present invention, 2.0 or more is preferable, and the color filter of the present invention can be produced, for example, as follows. First, after forming a transparent thin film as an adhesive layer on a polished / washed glass substrate, if necessary, use the dip method, coaters such as rollers, spin coating equipment such as whalers and spinners to repel ink. The composition solution that forms the black photosensitive resin layer is applied, dried, and cured if necessary to form a black photosensitive resin layer. Next, by a photochemical method, a so-called photolithography method, using a lamp such as a chemical lamp, a high-pressure mercury lamp, a mercury xenon lamp, and a metal halide lamp, by exposing through a mask of a predetermined pattern and developing, The black photosensitive resin layer in the uncured portion is removed to form the ink repellent black matrix. The mutual ratio and size of the removed portions of the black resin layer can be freely changed by adjusting the mask used for exposure.

In order to form an ink-repellent black matrix, the following means can be used.
First, after forming a transparent thin film as an adhesive layer on the polished and washed glass substrate as necessary, the dipping method,
An ink repellent black resin layer is formed by applying and drying a composition solution forming the ink repellent black resin layer and curing it as necessary using a coater such as a roller, a whaler, and a spin coater such as a spinner. . Furthermore, a dip method, a coater such as a roller, a spin coating device such as a whaler or a spinner is used to coat and dry the composition solution constituting the photosensitive resin layer. Next, exposure is performed through a mask having a predetermined pattern using a lamp such as a chemical lamp, a high pressure mercury lamp, a mercury xenon lamp, and a metal halide lamp by a photochemical method, so-called photolithography method. Then, the photosensitive resin layer is developed with a developing solution to remove the photosensitive resin layer into a predetermined pattern.
When a resin that dissolves in a photosensitive resin developer is selected as the ink-repellent black resin, the ink-repellent black resin layer can be etched simultaneously with the development of the photosensitive resin, and the ink-repellent black resin can be formed into a predetermined pattern. Can be removed. If the ink-repellent black resin does not dissolve in the photosensitive resin developer, use the resulting pattern of the photosensitive resin layer as a mask to etch with an ink-repellent black resin-soluble etchant, and then remove the photosensitive By removing the resin layer, it is possible to obtain a pattern in which the ink-repellent black resin layer is removed in a predetermined shape, that is, a black matrix having ink-repellent property.

In order to form an ink-repellent black matrix, the following means can be used.
First, after forming a transparent thin film as an adhesive layer on the polished and washed glass substrate as necessary, the dipping method,
Using a coater such as a roller, a whaler, a spin coater such as a spinner, a composition solution forming the black resin layer is applied, dried, and cured as necessary to form a black resin layer. Further, using a dipping method, a coater such as a roller, a whaler, a spin coater such as a spinner, a composition solution that forms a photosensitive resin layer containing an ink repellent component is applied and dried. Next, exposure is performed through a mask having a predetermined pattern using a lamp such as a chemical lamp, a high pressure mercury lamp, a mercury xenon lamp, and a metal halide lamp by a photochemical method, so-called photolithography method. Then, the photosensitive resin layer is developed with a developing solution to remove the photosensitive resin layer into a predetermined pattern.
When the black resin layer that is soluble in the photosensitive resin developer is selected, the black resin layer can be etched simultaneously with the development of the photosensitive resin, and the black resin can be removed in a predetermined pattern. If the black resin does not dissolve in the developing solution of the photosensitive resin, use the resulting photosensitive resin layer pattern as a mask to etch with an etching solution that dissolves the black resin to obtain a black matrix having ink repulsion. You can

The present invention is mainly intended to provide a color filter for a liquid crystal display device. The size of each pixel of the color filter is about 100 μm, and the line width of the light-shielding black matrix provided between each pixel is about 20 μm. These pixels may be a so-called stripe type in which they are arranged in a line, or a colored portion surrounded by a black matrix may be arranged in a grid.
Red, green, and blue are supplied to the areas subdivided by these ink-repellent black matrices by supplying a coloring agent such as a coloring ink by a printing method, an inkjet method, a photolithography method, or a dyeing component for dyeing the area. The three primary colors are formed to form pixels. To achieve the purpose of providing a color filter by subjecting the surface of the ink-repellent black matrix to water- and oil-repellency-free treatment to a substrate by heating or washing, and then applying a top coat agent and heat curing as necessary. is there.

In the case of coloring by a printing method, planographic offset printing using a waterless planographic printing plate is preferable from the viewpoint of printing accuracy, but it is not limited to this method. By these printing methods, the exposed portion of the substrate partitioned by the ink-repellent black matrix is colored with the inks of the three primary colors of red, green and blue.

When coloring by the ink jet method, a coloring ink containing a coloring component and a binder resin can be used. As the coloring component, it is preferable to use pigments and dyes having excellent heat resistance and light resistance. The binder resin is preferably a transparent resin having excellent heat resistance, and examples thereof include a melamine resin and an acrylic resin, but the binder resin is not limited thereto. Ink containing these components is jetted using an inkjet device to directly color the exposed portion of the substrate partitioned by the ink-repellent black matrix.

When an ink containing a dye is jetted by using an ink jet device to dye the exposed portion of the substrate, a dyeable medium is previously applied under the black resin layer if necessary. As the dyeable medium, it is preferable to select a material having a good affinity with the dye used. When an acid dye is used, for example, in addition to known natural polymer materials such as collagen, casein and gelatin, amino groups and 4
A synthetic polymer material such as an acrylic polymer and polyvinyl alcohol into which a quaternary ammonium salt is introduced is applied.
The dye used is not limited to an acid dye, but a basic dye, a direct dye, an oil-soluble dye, a reactive dye, or the like can be used. In that case, it is preferable to select, as the dyeable medium, one having a group capable of dyeing the dye used. An ink-repellent black matrix pattern is formed on these dyeable media by the above method.
Then, an ink containing a dye component is jetted onto the exposed portion of the dyeable medium partitioned by the ink repellent black matrix by an inkjet method to dye the dyeable medium layer into three primary colors of red, green and blue.

In the case of coloring by the photolithography method, a method of forming a predetermined pattern by using a photosensitive color paste, a method of applying a non-photosensitive color paste and then applying a photoresist, and etching the pixel There are forming methods, but the present invention is not limited to these methods. By these methods, the exposed portion of the substrate partitioned by the ink-repellent black matrix is colored into the three primary colors of red, green and blue.

When the substrate treatment for eliminating the water and oil repellency of the surface of the black matrix is carried out by heating, the colored portion is cured or fixed and then these colored substrates are decomposed or deactivated at a temperature not lower than the deactivation temperature. Heat to. When the substrate treatment is performed by washing, after curing or fixing the colored portion, these colored substrates are immersed in a solvent in which the black resin and the colored portion have resistance, and the ink repellent component is soluble, and then washed. dry.

The transparent substrate of the present invention is not particularly limited and, for example, glass, plastic film or sheet is preferably used.

The transparent thin film formed on the transparent substrate as necessary serves as a black resin layer and an adhesive layer for improving the adhesiveness between the pixel and the transparent substrate. For example, (N
Aminoalkylalkoxysilane derivatives such as -trimethoxysilylpropyl) polyethyleneimine can be used, but are not limited thereto.

The top coat is provided for the purpose of protecting and flattening the pixel portion. The top coat agent is preferably a transparent thermosetting resin having excellent heat resistance and chemical resistance, such as silica-based coating agent, acrylic resin, epoxy resin, silicone, or polyimide-based agent, whose viscosity and solid content are adjusted by a solvent. It is used, but is not limited to these. The coating is usually spin-coated on the entire surface substrate with a color filter, but the method is not limited to this method.

[0046]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A 0.2% by weight ethanol solution of (N-trimethoxysilpropyl) polyethyleneimine (PS076, manufactured by Chisso Corp.) was prepared as a primer solution. Spin on a glass substrate washed and dried with a spinner at 1500 rpm
m, applied for 10 seconds, and dried at 150 ° C. for 10 minutes to provide an adhesive layer. Then, a photocurable black photosensitive resin liquid having the following composition was spinned thereon with a spinner at a rotation speed of 5
After coating at 00 rpm for 2 seconds, then 1000 rpm for 10 seconds, prebaking was performed at 80 ° C. for 15 minutes.

[Black photosensitive resin liquid composition] Polymer 8.35 obtained by adding glycidyl methacrylate to a ternary acrylic copolymer composed of styrene / methyl methacrylate / methacrylic acid (3: 3: 4 (copolymerization ratio)). Parts by weight Trimethylolpropane triacrylate 3.00 parts by weight Epoxy acrylate 2.00 parts by weight "Irgacure" 369 (manufactured by Ciba-Gaigi) 0.59 parts by weight "Irgacure" 907 (manufactured by Ciba-Gaigi) 0.59 parts by weight Trithiophosphite 0.39 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 4.03 parts by weight Fluorine-based surfactant "EFTOP" EF-123A-1 (manufactured by Tochem Products Co., Ltd.) 0.70 parts by weight Fluorine-based Surfactant "MEGAFAC" F-179 (manufactured by Dainippon Ink and Chemicals, Inc.) .50 parts by weight of 2-butoxyethanol 76.85 parts by weight, and then vacuum contact a predetermined pattern mask, and developed with 2-aminoethanol 0.125% aqueous solution was 210 mJ / cm ² exposure in the chemical lamp, unexposed portions The black photosensitive resin layer of was removed. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes to form a layer having a thickness of 1.5 μm. By the above operation, the black resin black matrix having the function of the ink-repellent partition wall was formed on the glass substrate.

Inks of red, green, and blue were prepared in the following manner. First, 5 parts by weight of PR177 as a red pigment, 5 parts by weight of a surfactant "Newcol" 710F (manufactured by Nippon Emulsifier Co., Ltd.), and 79 parts by weight of water were added with glass beads, and stirred for 10 hours using a homogenizer. A pigment dispersion was prepared. Melamine resin (“Sumitec Resin” M-3, manufactured by Sumitomo Chemical Co., Ltd.) was added to 89 parts by weight of the above dispersion liquid.
1 part by weight of a curing agent (“Sumitex Accelerator” ACX manufactured by Sumitomo Chemical Co., Ltd.) was mixed to obtain a red ink for producing a color filter. Green ink (PG as pigment
36) and blue ink (using PB15 as a pigment) were prepared in the same manner.

The receding contact angle with respect to the ink repellent black matrix is 100.0 ° with respect to water, 50.0 ° with respect to the red ink, the green ink and the blue ink, respectively.
It was 50.0 ° and 20.0 °.

The ink having the above composition was jetted to the portions where the red, green and blue pixels were to be formed in the portion where the black resin layer was removed, by using an ink jet type ink jet device, and colored in each color.

After being colored with these inks, the ink is stored at 150 ° C. for 20 minutes.
The ink in the colored portion was thermoset by heating for minutes.

The ink was suitable for ink jet and could be jetted well. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

After heat-treating the substrate at 280 ° C. for 1 hour to eliminate water and oil repellency of the surface of the black matrix, a polyimide resin (“Semicofine” sp900, Toray) N-methylpyrrolidone 30 was used as a top coat.
The wt% solution was applied with a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Comparative Example 1 A 0.2% by weight ethanol solution of (N-trimethoxysilpropyl) polyethyleneimine (PS076, manufactured by Chisso Corporation) was prepared as a primer solution. Spin on a glass substrate washed and dried with a spinner at 1500 rpm
m, applied for 10 seconds, and dried at 150 ° C. for 10 minutes to provide an adhesive layer. Then, a photocurable black photosensitive resin liquid having the composition described in Example 1 was spun on the spinner at a rotation speed of 500 rpm for 2 seconds, and then 1000 rpm for 1 second.
After applying for 0 seconds, prebaking was performed at 80 ° C. for 15 minutes.

Next, in the same procedure as in Example 1, exposure, development,
Heat treatment was performed at 150 ° C. for 30 minutes to obtain a black resin plaque matrix having a thickness of 1.5 μm.

The ink having the above composition was jetted onto the portions of the portion where the black resin layer had been removed where red, green and blue pixels were to be formed, using an ink jet type ink jet device, and colored in each color.

After coloring with these inks, at 20 ° C., 20
The ink in the colored portion was thermoset by heating for minutes.

The ink was suitable for ink jet and could be jetted well. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

A 30 wt% N-methylpyrrolidone solution of a polyimide resin (“Semicofine” sp900, Toray) was applied as a top coat on the substrate with a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The topcoat had a step difference of 0.5 μm between the black resin black matrix portion and the pixel portion.

Example 2 In Example 1, a water-soluble photosensitive material having the following composition was previously coated on a glass substrate with a spinner, dried and then crosslinked by 210 mJ / cm ² whole surface exposure to a thickness of 10 μm.
m dyeable medium layer has been formed.

Composition of dyeable medium layer Low molecular weight gelatin (average molecular weight 20,000) 15 parts by weight Ammonium dichromate 2 parts by weight Water 85 parts by weight Then, black photosensitive resin was applied and dried by the same procedure as in Example 1. Exposure, development, and heat treatment were performed to form an ink-repellent black resin black matrix.

An ink containing an acid dye having the following composition (acid dyes used are Nippon Kayaku's Red 14P, Green 1P, and Blue 5P) is jetted on the dyeable medium layer surrounded by the partition wall by an ink jet device. And dyed red, blue and green.

Ink composition Acid dye 3 parts by weight Acetic acid 10 parts by weight Water 87 parts by weight Receding contact angle with respect to the black resin black matrix is 100.0 ° with respect to water, and with respect to the red ink, green ink and blue ink respectively 56.0 °, 58.0 °, 3
It was 0.0 °.

Repulsion of the ink by the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

The substrate was heat-treated at 280 ° C. for 1 hour to remove the water and oil repellency of the surface of the black matrix, and then N-methylpyrrolidone 30 of polyimide resin (“Semicofine” sp900, Toray) was used as a top coat.
The wt% solution was applied with a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 3 50 parts by weight of a cyclopentadiene resin having a softening point of 145 ° C. (“Nisseki Neo Resin” 540 manufactured by Nisseki Chemical Co., Ltd.), 5 parts by weight of an alkyd resin, and a petroleum solvent (manufactured by Nippon Oil Co., Ltd.) 5
No. solvent) (45 parts by weight) was mixed under a nitrogen stream, heated and heated to 200 ° C. for 1 hour with stirring to obtain a varnish A. 80 parts by weight of this varnish A and phthalocyanine blue 2
A blue ink was obtained by kneading 0 parts by weight with a triple roll. Phthalocyanine green was used for green ink, and Brilliant Carmine 6B was used for red ink.

The receding contact angle of the black resin black matrix prepared in Example 1 was 10 with respect to water.
0.0 °, and 48.0 °, 48.0 °, and 20.0 ° for the above red ink, green ink, and blue ink, respectively.

Of the black resin-removed portion of the glass substrate with black resin black matrix described in Example 1, red,
Pixel portions corresponding to green, blue and each color were sequentially printed in each color using the above ink and "Toray waterless lithographic planographic offset printing" and colored. The ink had good waterless printability, the black matrix exhibited sufficient repulsion, and bleeding, squeezing out, and mixing of each color were not observed.

After heat-treating the substrate at 280 ° C. for 1 hour to remove the water and oil repellency of the surface of the black matrix, a polyimide resin (“Semicofine” sp900, Toray) N-methylpyrrolidone 30 was used as a top coat.
The wt% solution was applied with a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 4 A photocurable black photosensitive resin liquid having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rp.
m, 10 seconds, then 3000 rpm for 30 seconds, and then prebaked at 80 ° C. for 30 minutes.

[Black photosensitive resin liquid composition] Photocurable polyimide "Photo Nice" UR-3100 (manufactured by Toray Industries, Inc.) 10 parts by weight polyvinylidene fluoride 5 parts by weight Carbon Black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 5 Parts by weight N-methylpyrrolid 80 parts by weight Next, a predetermined pattern mask is vacuum-contacted and exposed to 200 mJ / cm ² with a chemical lamp, and then “Photonice” developer DV-605 (manufactured by Toray Industries, Inc.) is used for 23 parts. Developed at ° C.

After development, rinsing was performed with isopropanol. Then, heat treatment was performed at 150 ° C. for 30 minutes. By the above operation, the ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 70.0 ° with respect to water, 25.0 ° with respect to the red ink, green ink and blue ink described in Example 1, and 22. It was 0 ° and 20.0 °.

The ink described in Example 1 was applied to the areas of the removed black resin layer where red, green and blue pixels were to be formed, using an ink jet type ink injection device, and colored in the respective colors. . The ink was suitable for inkjet, and good ejection was possible. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

After coloring with these inks, the ink was stored at 150 ° C. for 20 minutes.
The ink in the colored portion was thermoset by heating for minutes. Then, in a nitrogen atmosphere, from 150 ° C to 300 ° C for 3-5
The temperature is raised at ℃ / min, and the polyimide cure is performed at 300 ℃ for 30 minutes as well as the heat treatment (substrate treatment to eliminate the water and oil repellency of the black matrix surface), and the thickness is 1.5 μm.
Layers.

A 30 wt% N-methylpyrrolidone solution of a polyimide resin (“Semicofine” sp900, Toray) was applied as a top coat by a spinner. 10 after application
After drying at 0 ° C. for 10 minutes, it was heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. As a result of measuring the color unevenness of each pixel with a microspectroscope, the color difference is ΔE ≦ 3
And obtained a high quality color filter.

Example 5 A 0.2% by weight ethanol solution of (N-trimethoxysilpropyl) polyethyleneimine (PS076, manufactured by Chisso Corporation) was prepared as a primer solution. Spin on a glass substrate washed and dried with a spinner at 1500 rpm
m, applied for 10 seconds, and then dried at 150 ° C. for 10 minutes to provide a contact layer. Then, a photocurable black photosensitive resin liquid having the following composition was spinned thereon with a spinner at a rotation speed of 5
After coating at 00 rpm for 2 seconds, then 1000 rpm for 10 seconds, prebaking was performed at 80 ° C. for 15 minutes.

[Black photosensitive resin liquid composition] Polymer 8.35 obtained by adding glycidyl methacrylate to a ternary acrylic copolymer composed of styrene / methyl methacrylate / methacrylic acid (3: 3: 4 (copolymerization ratio)). Parts by weight Trimethylolpropane triacrylate 3.00 parts by weight Epoxy acrylate 2.00 parts by weight "Irgacure" 369 (manufactured by Ciba-Gaigi) 0.59 parts by weight "Irgacure" 907 (manufactured by Ciba-Gaigi) 0.59 parts by weight Trithiophosphite 0.39 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 4.03 parts by weight Polytetrafluoroethylene fine particles "Lubron" LD-100 (manufactured by Daikin Industries, Ltd.) 1.40 parts by weight 2-Butoxyethanol 79 .65 parts by weight Next, a predetermined pattern mask is vacuum-bonded, and a chemical lamp is used. 210 mJ / cm ² and developed with 2-aminoethanol 0.125% aqueous solution after exposure to remove the black photosensitive resin layer in the unexposed portion. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes to form a layer having a thickness of 1.5 μm. By the above operation, the ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 75.0 ° with respect to water, and 46.0 ° and 48. with respect to the red ink, the green ink and the blue ink described in Example 1, respectively. It was 0 ° and 20.0 °.

The ink described in Example 1 was applied to the areas where red, green and blue pixels were to be formed in the areas where the black resin layer had been removed by using an ink jet type ink ejecting device, and colored in respective colors. .

After coloring with these inks, the ink was stored at 150 ° C. for 20 minutes.
The ink in the colored portion was thermoset by heating for minutes.

The ink was suitable for ink jet, and good jetting was possible. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

The substrate was heated at 280 ° C. for 1 hour to remove the water and oil repellency of the surface of the black matrix, and then an acrylic top coat agent was applied as a top coat by a spinner. After coating, it was dried at 90 ° C. for 10 minutes, and then heated and cured at 200 ° C. for 60 minutes. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 6 A black resin solution having the following composition was applied onto a washed and dried glass substrate with a spinner at a rotation speed of 500 rpm for 2 seconds and then 1000 rpm for 10 seconds. 30 at 150 ° C
After heat-drying for minutes, a photosensitive resin liquid having the following composition was applied with a spinner at 1000 rpm for 10 seconds, and heat-dried at 80 ° C. for 10 minutes.

[Black Resin Liquid Composition] Polyimide “Semicofine” sp710 (manufactured by Toray Industries, Inc.) 30 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 15 parts by weight N-methylpyrrolidone 40 parts by weight [Photosensitive resin Liquid composition] Positive photoresist (Shipley "Micropsit" RC100 30CP) 100 parts by weight Solvent (Shipley Thinner C) 45 parts by weight Silicone fine particles "Tospearl" (manufactured by Toshiba Silicone Co., Ltd.) 5 parts by weight Next, a predetermined pattern mask is applied. After vacuum contact and exposure with a chemical lamp for 1 minute, Shipy "Micropsi"
It was developed with a developing solution of t ″ Deveroper / water = 1/5. At this time, the black resin layer was etched simultaneously with the development of the photosensitive resin layer by the developing solution, and an ink-repellent black resin black matrix was formed on the glass substrate. Been formed.

The receding contact angle with respect to the black black matrix produced by the above procedure is 70.0 ° with respect to water, and 25.0 ° and 22.0 with respect to the red ink, the green ink and the blue ink described in Example 1, respectively. Was 20.0 °.

The ink described in Example 1 was applied to the areas where the red, green, and blue pixels were to be formed in the removed portions of the black resin layer, using an ink jet type ink jet device, and colored in the respective colors. Then, the ink in the colored portion was thermally cured by heating at 150 ° C. for 20 minutes. Subsequently, the black matrix was cured, and at the same time, a heat treatment was performed at 300 ° C. for 30 minutes to eliminate the water and oil repellency of the surface of the black matrix.

The ink was suitable for ink jet and could be jetted well. The ink repulsion property of the black matrix was good, and bleeding, protrusion, and mixing of each color were not observed.

A 30 wt% N-methylpyrrolidone solution of a polyimide resin (“Semicofine” sp900, Toray) was applied as a top coat by a spinner. 10 after application
After drying at 0 ° C. for 10 minutes, it was heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 7 A 0.2% by weight ethanol solution of (N-trimethoxysilpropyl) polyethyleneimine (PS076, manufactured by Chisso Corporation) was prepared as a primer solution. Spin on a glass substrate washed and dried with a spinner at 1500 rpm
m, applied for 10 seconds, and dried at 150 ° C. for 10 minutes to provide an adhesive layer. Next, a photodissolving black photosensitive resin solution having the following composition was applied and dried in hot air at 60 ° C. to form a photosensitive resin layer having a thickness of 2 μm.

[Black photosensitive resin solution composition] Naphthoquinone 1,2-diazide 5-sulfonic acid ester of phenol novolac resin ("Sumiresin" PR50235 manufactured by Sumitomo Bakelite) having an esterification degree of 45%, molecular weight: about 1300) 10. 0 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 3.5 parts by weight Fluorosurfactant "EFTOP" EF-123A-1 (manufactured by Tochem Products Co., Ltd.) 0.7 parts by weight Fluorosurfactant Agent "MEGAFAC" F-179 (manufactured by Dainippon Ink and Chemicals, Inc.) 3.5 parts by weight 1,4-dioxane 82.3 parts by weight Next, a predetermined pattern mask was vacuum-adhered to 210 mJ / with a chemical lamp. After the exposure, the black photosensitive resin layer in the exposed area was removed by developing with a ² wt% NaOH aqueous solution. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes. By the above operation, an ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 100.0 ° with respect to water,
The red ink, the green ink, and the blue ink described in Example 1 were 50.0 °, 50.0 °, and 20.0 °, respectively.

An ink having the same composition as in Example 1 was jetted onto the portions of the portion where the black resin layer had been removed where red, green and blue pixels were to be formed by using an ink jet type ink jet device, and the respective colors were jetted. Colored.

After coloring these inks, the ink in the colored portion was thermally cured by heating at 150 ° C. for 20 minutes.

The ink was suitable for ink jet and could be jetted well. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

The substrate was washed with ethanol and dried to remove the water and oil repellency of the surface of the black matrix, and a polyimide resin (“Semicofine” sp
900 wt% Toray) N-methylpyrrolidone 30 wt% solution was applied by a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 8 A photo-dissolving black photosensitive resin liquid having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rp.
m, 10 seconds, then 3000 rpm for 30 seconds, and then prebaked at 80 ° C. for 30 minutes.

[Black photosensitive resin liquid composition] 10 parts by weight of light-soluble polyimide

[Chemical 3] Polyvinylidene fluoride 5 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 5 parts by weight N-methylpyrrolidone 80 parts by weight Next, a predetermined pattern mask was vacuum-adhered and exposed with a chemical lamp at 200 mJ / cm ² and then NaOH ² wt. % Aqueous solution to remove the black photosensitive resin layer in the exposed area. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes. By the above operation, the ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 70.0 ° with respect to water, 25.0 ° with respect to the red ink, the green ink and the blue ink described in Example 1, and 22. It was 0 ° and 20.0 °.

The ink having the same composition as in Example 1 was jetted onto the portions of the portion where the black resin layer was removed where red, green and blue pixels were to be formed by using an ink jet type ink jet device, and the respective colors were jetted. Colored. The ink was suitable for inkjet, and good ejection was possible. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

After coloring these inks, the ink in the colored portion was thermally cured by heating at 150 ° C. for 20 minutes.
Then, from 150 ° C to 300 ° C in a nitrogen atmosphere at 3-5 ° C /
Heat treatment at 300 ° C for 30 minutes by raising the temperature in min (substrate treatment to eliminate the water and oil repellency of the black matrix surface)
Polyimide cure that also serves as the above was performed to form a black matrix layer having a thickness of 1.5 μm.

20 wt% of silica-based coating agent propylene glycol monomethyl ether as a top coat
% Solution was applied with a spinner. 10 at 100 ° C after coating
After minute drying, it was heated at 300 ° C. for 1 hour to cure. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 9 A 0.2% by weight ethanol solution of (N-trimethoxysilpropyl) polyethylenein (PS076, manufactured by Chisso Corp.) was prepared as a primer solution. Spin on a glass substrate washed and dried with a spinner at 1500 rpm
m, applied for 10 seconds, and dried at 150 ° C. for 10 minutes to provide an adhesive layer. Next, a photodissolving black photosensitive resin solution having the following composition was applied and dried in hot air at 60 ° C. to form a photosensitive resin layer having a thickness of 2 μm.

[Black Photosensitive Resin Liquid Composition] Naphthoquinone 1,2-diazide 5-sulfonic acid ester of phenol novolac resin (“Sumiresin PR50235” manufactured by Sumitomo Bakelite) having an esterification degree of 45%, molecular weight: about 1300) 10. 0 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 3.5 parts by weight Tetrafluoroethylene fine particles "LUBRON" LD-100 (manufactured by Daikin Industries, Ltd.) 1.4 parts by weight 1,4-dioxane 85. 1 part by weight Next, a predetermined pattern mask was vacuum-contacted, exposed to 210 mJ / cm ² with a chemical lamp, and developed with a ² wt% NaOH aqueous solution to remove the black photosensitive resin layer in the exposed part. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes. By the above operation, the ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black black matrix produced by the above procedure is 75.0 ° with respect to water, and 46.0 ° and 48.0 with respect to the red ink, the green ink and the blue ink described in Example 3, respectively. Was 20.0 °.

Of the black resin-removed portion of the glass substrate with the black resin black matrix having the above composition, red,
Pixel portions corresponding to each color of green, blue and each color were sequentially printed and colored in each color using planographic offset printing using the ink described in Example 3 and "Toray waterless planographic printing". The ink had good waterless printability, black matrix showed sufficient resilience, bleeding, squeezing out, and mixing of each color was not observed.

The substrate was heated at 300 ° C. for 1 hour to remove the water and oil repellency of the surface of the black matrix, and then an acrylic top coat agent was applied as a top coat with a spinner. After coating, it was dried at 90 ° C. for 10 minutes, and then heated and cured at 200 ° C. for 60 minutes. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

Example 10 A photo-dissolving black photosensitive resin liquid having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rp.
m, 10 seconds, then 3000 rpm for 30 seconds, and then prebaked at 80 ° C. for 30 minutes.

[Black photosensitive resin liquid composition] Light-soluble polyimide (described in Example 8) 10 parts by weight Silicone fine particles "Tospearl" (manufactured by Toshiba Silicone Co., Ltd.) 5 parts by weight Carbon black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) ) 5 parts by weight N-methylpyrrolidone 80 parts by weight Next, a predetermined pattern mask is vacuum-contacted, exposed to a chemical lamp at 200 mJ / cm ² and developed with a ² wt% NaOH aqueous solution to remove the black photosensitive resin layer in the exposed part. did. Subsequently, heat treatment was performed at 150 ° C. for 30 minutes. By the above operation, the ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 70.0 ° with respect to water, 25.0 ° with respect to the red ink, the green ink and the blue ink described in Example 1, and 22. It was 0 ° and 20.0 °.

An ink having the same composition as in Example 1 was jetted onto the portions where the red, green, and blue pixels of the portion where the black resin layer was removed are to be formed, using an ink jet type ink jet device, and the respective colors were jetted. Colored.

After coloring with these inks, the ink was stored at 150 ° C. for 20 minutes.
The ink in the colored portion was thermoset by heating for minutes. Then, in a nitrogen atmosphere, from 150 ° C to 300 ° C for 3-5
Heat treatment at 300 ° C for 30 minutes to raise the water / oil repellency of the surface of the black matrix,
The black matrix was a layer having a thickness of 1.5 μm.

The ink was suitable for ink jet, and good jetting was possible. Ink resilience of the black resin black matrix was good, and bleeding, squeezing out, and mixing of each color were not observed.

An acrylic top coat agent was applied as a top coat by a spinner. After coating, it was dried at 90 ° C. for 10 minutes, and then heated and cured at 200 ° C. for 60 minutes. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦ 3 as a color difference.
And obtained a high quality color filter.

Example 11 An ink-repellent black resin liquid having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rp.
m, 2 seconds, then 1000 rpm for 10 seconds, 8
Heat at 0 ° C. for 15 minutes.

[Ink Repellent Black Resin Liquid Composition] Epoxy Resin (Mitsui Petrochemical Co., Ltd. “Epomic” R301) 30 parts by weight Carbon Black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 20 parts by weight Fluorosurfactant “EFTOP” "EF-123A-1 (manufactured by Tochem Products Co., Ltd.) 3 parts by weight Fluorosurfactant" MEGAFAC "F-179 (manufactured by Dainippon Ink and Chemicals, Inc.) 100 parts by weight Next, on it The photosensitive resin liquid having the composition is applied to the spinner by a spinner at 1000 rpm for 10 seconds, and the temperature is 80 °
Then, it was dried by heating for 30 minutes.

[Photosensitive resin solution composition] Positive photoresist (Shipley "Micropsit" RC100 30CP) 100 parts by weight Solvent (Shipley Thinner C) 43 parts by weight Next, a predetermined pattern mask is vacuum-adhered, and a chemical lamp is used for 1 minute. After exposure, Shipey "Micropsi"
Development was carried out with a developing solution of t ″ Deveroper / water = 1/5 to obtain a pattern of the photosensitive resin layer. Next, the ink-repellent black resin layer in the portion where the photosensitive resin layer was removed was etched with toluene to give a predetermined pattern. The ink-repellent black resin was removed in the pattern of 1. The photosensitive resin layer was removed with a 5% aqueous sodium hydroxide solution, and then heat-cured at 150 ° C. for 20 minutes to obtain an ink-repellent black resin black matrix on the glass substrate. It was

The receding contact angle with respect to the black resin black matrix produced by the above procedure is 100.0 ° with respect to water,
The red ink, the green ink, and the blue ink described in Example 1 were 50.0 °, 50.0 °, and 20.0 °, respectively.

An ink having the same composition as in Example 1 was jetted onto the portions of the portion where the black resin layer had been removed where red, green and blue pixels were to be formed, using an ink jet type ink jet device, and the respective colors were jetted. Colored.

After coloring with these inks, at 20 ° C., 20
The ink in the colored portion was thermoset by heating for minutes.

The ink was suitable for ink jet, and good jetting was possible. Ink-repellent resin The black matrix had a good ink-repellent property, and bleeding, squeezing out, and mixing of each color were not observed.

After washing the substrate with isopropanol and drying it to remove the water and oil repellency of the surface of the black matrix,
Polyimide resin (“Semicofine” sp900, Toray) 30 wt% N-methylpyrrolidone as top coat
% Solution was applied with a spinner. 10 at 100 ° C after coating
After minute drying, heat treatment was performed at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3, and a high quality color filter was obtained.

Example 12 A black resin liquid having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rpm for 2 seconds and then 1000 rp.
m, applied for 10 seconds. After heating and drying at 150 ° C for 30 minutes, add a photosensitive resin solution of the following composition to 1000 rpm with a spinner.
The coating was applied for 10 seconds and dried by heating at 80 ° C for 10 minutes.

[Black Resin Liquid Composition] Polyimide “Semicofine” sp710 (manufactured by Toray Industries, Inc.) 30 parts by weight Carbon Black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 15 parts by weight N-methylpyrrolidone 40 parts by weight [Photosensitive] Resin composition] Positive photoresist (Tokyo Ohka 6030) 52.1 parts by weight Solvent (Shipley Thinner C) 41.0 parts by weight Fluorosurfactant "EFTOP" EF-123A-1 (manufactured by Tochem Products Co., Ltd.) 0.4 Part by weight Fluorine-based surfactant "MEGAFAC" F-179 (manufactured by Dainippon Ink and Chemicals, Inc.) 6.5 parts by weight Next, a predetermined pattern mask is vacuum-contacted and exposed with a chemical lamp for 1 minute, and then Shipley "Microposit "Deveroper /
It was developed with a water = 1/6 developer. At this time, the black resin layer was also etched by the developing solution at the same time as the development of the photosensitive resin layer, and an ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angles with respect to the black resin black matrix produced by the above procedure are 70.0 ° with respect to water, and 25.0 °, 22.0 ° and 20.0 ° with respect to the red ink, the green ink and the blue ink described in Example 1, respectively. there were.

The ink described in Example 1 was applied to the areas where the red, green and blue pixels were to be formed in the areas where the black resin layer had been removed by using an ink jet type ink ejecting device, and colored in the respective colors. Then, the ink in the colored portion was thermoset by heating at 150 ° C. for 20 minutes. Subsequently, heat treatment was performed at 300 ° C. for 30 minutes to cure the black matrix and simultaneously subject the substrate to treatment to eliminate the water and oil repellency of the black matrix surface.

The ink was suitable for ink jet, and good jetting was possible. The ink repulsion property of the black matrix was good, and bleeding, protrusion, and mixing of each color were not observed.

As a top coat, a 30 wt% N-methylpyrrolidone solution of a polyimide resin (“Semicofine” sp900, Toray) was applied by a spinner. 10 after application
After drying at 0 ° C. for 10 minutes, it was heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦ 3 as a color difference.
And obtained a high quality color filter.

Example 13 A black resin solution having the following composition was spun on a washed and dried glass substrate with a spinner at a rotation speed of 500 rpm for 2 seconds and then 1000 rp.
m, applied for 10 seconds. After heating and drying at 150 ° C for 30 minutes, add a photosensitive resin solution of the following composition to 1000 rpm with a spinner.
The coating was applied for 10 seconds and dried by heating at 80 ° C for 10 minutes.

[Black Resin Liquid Composition] Polyimide “Semicofine” sp710 (manufactured by Toray Industries, Inc.) 30 parts by weight Carbon Black MA100 (manufactured by Mitsubishi Kasei Co., Ltd.) 15 parts by weight N-methylpyrrolidone 40 parts by weight [Photosensitive] Resin Composition] Positive photoresist (Shipley "Microposit" RC100 30CP) 70 parts by weight Solvent (Shipley Thinner C) 30 parts by weight Fluorosurfactant "EFTOP" EF-123A-1 (manufactured by Tochem Products Co., Ltd.) ) 0.70 parts by weight Fluorine-based surfactant "MEGAFAC" F-179 (manufactured by Dainippon Ink and Chemicals, Inc.) 3.50 parts by weight Next, a predetermined pattern mask is vacuum-adhered and exposed with a chemical lamp for 1 minute, and then Shipley "Microposit" Deveroper /
It was developed with a water = 1/6 developer. At this time, the black resin layer was also etched by the developing solution at the same time as the development of the photosensitive resin layer, and an ink-repellent black resin black matrix was formed on the glass substrate.

The receding contact angle with respect to the black resin black matrix produced by the above procedure was 70.0 ° with respect to water, and 25.0 °, 22.0 ° and 20.0 ° with respect to the red ink, the green ink and the blue ink described in Example 1, respectively. there were.

The ink described in Example 1 was applied to the areas where the red, green and blue pixels were to be formed in the areas where the black resin layer had been removed by using an ink jet type ink ejecting device, and colored in the respective colors. Then, the ink in the colored portion was thermoset by heating at 150 ° C. for 20 minutes.

The ink was suitable for ink jet, and good jetting was possible. The ink repulsion property of the black matrix was good, and bleeding, protrusion, and mixing of each color were not observed.

The substrate was washed with ethanol and dried to remove the water and oil repellency of the surface of the black matrix, and a polyimide resin (“Semicofine” sp.
900 wt% Toray) N-methylpyrrolidone 30 wt% solution was applied by a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured by a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦ 3 as a color difference.
And obtained a high quality color filter.

Example 14 As a varnish for coloring a pixel portion, 10.0 parts by weight of an acrylic resin precursor solution, 0.5 parts by weight of Brilliant Carmine 6B and 7.0 parts by weight of a solvent were kneaded to obtain a red varnish. It was prepared using phthalocyanine green for green varnish and phthalocyanine blue for blue varnish.

The receding contact angle of the black resin black matrix produced in Example 1 was 100.0 with respect to water.
°, 34.0 each for the red, green and blue varnishes above
They were °, 32.0 ° and 20.0 °.

The glass substrate with a black resin black matrix described in Example 1 was coated with the first color of the above varnish with a spinner and prebaked at 80 ° C. for 10 minutes.
Spin a photosensitive resin liquid of the following composition with a spinner at 1000 rpm, 10
It was applied for 2 seconds and heated and dried at 80 ° C. for 10 minutes.

[Photosensitive resin liquid composition] Positive photoresist (Shipley "Microposit" RC100 30CP) 70 parts by weight Solvent (Shipley Thinner C) 30 parts by weight Next, a predetermined pattern mask is vacuum-adhered, and a chemical lamp is used for 1 minute. After exposure, Shipley "Microposit" Deveroper /
It was developed with a water = 1/6 developer. At this time, at the same time as the development of the photosensitive resin layer with the developing solution, the lower layer was also patterned by etching to color the pixel portion corresponding to the first color. The layer was post-baked at 150 ° C for 30 minutes. Similarly, the second color and the third color were formed. The varnish repulsion of the black resin black matrix was good, and it was possible to form a highly accurate pixel pattern having no step on the black matrix.

After heat-treating the substrate at 280 ° C. for 1 hour to eliminate the water and oil repellency of the black matrix surface, a polyimide resin (Semicofine sp900, Toray) N-methylpyrrolidone 30 wt% was used as a top coat.
The solution was applied with a spinner. After coating, it was dried at 100 ° C. for 10 minutes and then heated at 280 ° C. for 1 hour to complete the imidization reaction. The top coat could be applied evenly.

When the step difference between the pixels was measured with a stylus type film thickness meter, the maximum film thickness difference was 0.2 μm. The result of measuring the color unevenness of each pixel with a microspectroscope is ΔE ≦
3 and a high quality color filter was obtained.

[0155]

As described above, according to the present invention, it is possible to provide a color filter in which ink bleeding and color mixing are surely prevented in manufacturing a color filter and which has sufficient flatness. This makes it possible to obtain a very high-precision color filter by using a printing method or an inkjet method.

Claims (24)

[Claims] 1. A method of manufacturing a color filter in which pixels of a plurality of colors are formed at predetermined positions on a transparent substrate, and a black matrix is formed in the gaps between the pixels. A method of manufacturing a color filter, comprising a step of treating the substrate to eliminate the water / oil repellency after forming the oil filter to have oil repellency. 2. The color according to claim 1, wherein a pixel is formed by using a colored ink after forming a black matrix having a water-repellent / oil-repellent surface using an ink repellent resin composition. Filter manufacturing method. 3. The color filter according to claim 2, wherein the surface of the black matrix has an ink repulsion property having a receding contact angle of 20 ° or more with respect to a coloring ink for forming pixels at the time of forming pixels. Manufacturing method. 4. The method of manufacturing a color filter according to claim 1, wherein the substrate treatment is heat treatment. 5. The method of manufacturing a color filter according to claim 1, wherein the substrate treatment is a treatment with a solvent. 6. The solvent used in the substrate treatment is water repellent
The method for producing a color filter according to claim 5, wherein the component having oil repellency is dissolved. 7. The method of manufacturing a color filter according to claim 6, wherein the solvent used for treating the substrate is ethanol. 8. The method for producing a color filter according to claim 6, wherein the solvent used for treating the substrate is isopropanol. 9. The method for producing a color filter according to claim 2, wherein the ink-repellent resin composition constituting the black matrix contains a fluorine-containing compound and / or a silicon-containing compound. 10. The method for producing a color filter according to claim 9, wherein the fluorine-containing compound is a monomer or oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group. 11. A monomer or oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group is represented by the general formula Rf-X-Rf ', or the general formula (Rf-XR) -Y- (R'-X. 11. A compound represented by "-Rf").
A method for manufacturing the described color filter. (Where Rf and R
f'represents a fluoroalkyl group, R and R'represent an alkylene group, and Rf and Rf 'may be the same or different. Also, X, X 'and Y are -COO-,-OCOO-,-CONR "
-,-OCONR "-,-SO2NR"-,-CONH-, SO2-,-SO2O-,-O-,-NR "-,-
Represents one of S-,-CO-,-OSO2O-,-OPO (OH) O-,
X, X'and Y may be the same or different. R "represents an alkyl group or hydrogen.) 12. The method for producing a color filter according to claim 9, wherein the fluorine-containing compound is a polymer compound having a fluorine atom. 13. A polymer compound having a fluorine atom,
The black matrix is contained in a dissolved state or a mixed state in a molecular order, wherein the black matrix is contained.
2. The method for manufacturing a color filter according to 2. 14. A polymer compound having a fluorine atom,
The method for producing a color filter according to claim 11, wherein the black matrix contains the fine particles in a dispersed state. 15. The method for producing a color filter according to claim 9, wherein the silicon-containing composition is fine silicone particles. 16. The method for producing a color filter according to claim 15, wherein the silicone fine particles are contained in a black matrix in a dispersed state. 17. The method for producing a color filter according to claim 1, wherein the black matrix contains a polymer of acrylic acid, methacrylic acid or an esterified product thereof. 18. The method of manufacturing a color filter according to claim 1, wherein the black matrix contains a polyimide resin. 19. The method for producing a color filter according to claim 1, wherein the black matrix contains a melamine resin. 20. The method for producing a color filter according to claim 2, wherein the ink-repellent resin composition contains a resin having a naphthoquinonediazide group. 21. A method of coloring with a coloring ink comprises:
The method of manufacturing a color filter according to claim 2, wherein the method uses an ink jet type ink jet device. 22. A method of coloring using a coloring ink,
The method for producing a color filter according to claim 2, wherein the method is a photolithography method. 23. A method of coloring with a coloring ink comprises:
The method of manufacturing a color filter according to claim 2, wherein the method is a printing method. 24. A method of manufacturing a color filter for liquid crystal display according to claim 1.